不同温度条件下氨氮在砂土中的吸附实验研究

温度的变化能够改变水体的环境,引起周围环境中的离子吸附解吸作用的变化。不同于其他土壤,砂土的保水保肥能力更差,砂土地区一旦发生氨氮(NH₄⁺-N)污染,情况会更加严重和突出。为防治砂土地区N H₄⁺-N污染提供理论依据与技术支持,通过N H₄⁺-N的静态吸附试验,研究不同温度条件下N H₄⁺N在粗砂、中砂、细砂中的吸附转化特征,得到如下结论: 在试验设置的温度区间内,总的趋势是温度越低,砂土对N H₄⁺-N的吸附量越高,表明温度升高对N H₄⁺-N的吸附有抑制作用,这主要是因为吸附过程中会产生弱放热效应,进而降低渗滤介质对N H₄⁺N的平衡吸附量; 在25~30 ℃区间内存在硝化与反硝化作用的临界温度,当温度低于临界温度时,N H₄⁺-N吸附量的减少主要是由于发生了硝化反应,当温度高于临界温度时,N H₄⁺-N的吸附量减少主要是由于发生了反硝化反应。     

The Effects of Varying Salinity on Ammonium Exchange in Estuarine Sediments of the Parker River,Massachusetts

We examined the effects of seasonal salinity changes on sediment ammonium (NH₄ ⁺) adsorption and exchange across the sediment–water interface in the Parker River Estuary, by means of seasonal field sampling, laboratory adsorption experiments, and modeling. The fraction of dissolved NH₄ ⁺ relative to adsorbed NH₄ ⁺ in oligohaline sediments rose significantly with increased pore water salinity over the season. Laboratory experiments demonstrated that small (∼3) increases in salinity from freshwater conditions had the greatest effect on NH₄ ⁺ adsorption by reducing the exchangeable pool from 69% to 14% of the total NH₄ ⁺ in the upper estuary sediments that experience large (0–20) seasonal salinity shifts. NH₄ ⁺ dynamics did not appear to be significantly affected by salinity in sediments of the lower estuary where salinities under 10 were not measured. We further assessed the importance of salinity-mediated desorption by constructing a simple mechanistic numerical model for pore water chloride and NH₄ ⁺ diffusion for sediments of the upper estuary. The model predicted pore water salinity and NH₄ ⁺ profiles that fit measured profiles very well and described a seasonal pattern of NH₄ ⁺ flux from the sediment that was significantly affected by salinity. The model demonstrated that changes in salinity on several timescales (tidally, seasonally, and annually) can significantly alter the magnitude and timing of NH₄ ⁺ release from the sediments. Salinity-mediated desorption and fluxes of NH₄ ⁺ from sediments in the upper estuary can be of similar magnitude to rates of organic nitrogen mineralization and may therefore be important in supporting estuarine productivity when watershed inputs of N are low.     

Coupling short-time sequencing batch reactor and coagulation–settling process for co-treatment of landfill leachate with raw municipal wastewater

The co-treatment of landfill leachate (LFL) with municipal wastewater (MWW) using shortcut sequencing batch reactor combined with coagulation–settling process (SBR + CS) was investigated. Four ratios of LFL to MWW volume (v/v) were used during experiments including the ratios 1:9, 2:8, 3:7 and 5:5. The average quality of the LFL was chemical oxygen demand (COD) of 20,800 mg L^?1 and NH₄-N of 2,645 mg L^?1. The SBR-treating LFL in six series where mixing aeration and settling phases were varied from 4 to 14 h was combined with coagulation (FeCl₃, Al₂(SO₄)₃) with an interval of 2 h. It was found that ratio (1:9) of leachate to MWW under aeration and mixing phase of 4 h with settling time of 1.5 h exhibited the highest ability to remove both COD and NH ₄ ⁺ -N, 99% and 85%, respectively. The short-time sequential batch reactor was tested for the treatment of raw LFL, and only 47% and 23% removal of COD and NH ₄ ⁺ -N, respectively, could be achieved.     

Quantifying Sediment Nitrogen Releases Associated with Estuarine Dredging

Experimental studies of sediment pore water NH₄ ⁺ chemistry, adsorbed NH₄ ⁺ concentrations, sediment?Cwater NH₄ ⁺ exchange and N₂?CN flux were carried out to quantify the mass of labile N that can be released during large-scale dredging activities. Pore water NH₄ ⁺ concentrations below 0.5-m sediment depth averaged 5 ± 2 mmol L^?1 with average adsorbed NH₄ ⁺ concentrations of 11 ??mol g^?1. Elevated NH₄ ⁺ concentrations found in rapidly accreting dredge channels are partly a result of the rapid advective burial of both reactive organic matter and pore water. Elutriate tests, a dilution of sediment with site water, yielded adsorbed NH₄ ⁺ concentrations very similar to those using the more typical KCl extraction. Intact deep sediment sections exposed to overlying water, used to simulate postdredging conditions, showed high initial fluxes of ammonium and no development of coupled nitrification?Cdenitrification under the cold incubation conditions. Despite high concentrations and effluxes of NH₄ ⁺ during dredging, the amount of NH₄ ⁺ release during dredging was <0.5% of northern Chesapeake Bay sediment fluxes. The likelihood of large environmental effects of nitrogen release during the dredging of navigational channels in the Chesapeake Bay is low.     

Identification of river water pollution characteristics based on projection pursuit and factor analysis

Human activities contribute different pollutants to receiving waters, often with significant variations in time and space. Therefore, integrating multiple parameters of water quality and their spatiotemporal variations is necessary to identify the pollution characteristics. Based on the water quality monitoring data with 12 parameters for 2 years at 22 sampling sites in the Cao-E River system, eastern China, the projection pursuit method was used to project all parameters and their temporal variations into a one-dimensional vector through two projections. Accordingly, we could easily assess the comprehensive water quality in different sampling sites and then classify their water pollution features. Factor analysis was then used to identify the pollution characteristics and potential sources. Results showed that all sampling sites for the river system could be classified into four groups: headwater sites (HS), agricultural nonpoint sources pollution sites (ANPS), point sources pollution sites (PSPS), and mixed sources pollution sites. Water quality in HS was good, containing only a few nutrients from the woodland runoff and soil erosion. For ANPS, the main pollutants were dissolved phosphorus, total P, and nitrate nitrogen (NO₃ ^?-N), mainly from farming land. For PSPS, ammonium nitrogen (NH₄ ⁺-N) and organic pollutants originated from industrial and municipal sewage. In HS and ANPS, NO₃ ^?-N was the main form of nitrogen, and a high ratio of NO₃ ^?-N/NH₄ ⁺-N was a remarkable characteristic, whereas NH₄ ⁺-N was the main form of nitrogen in PSPS. Except in HS, water quality in the other groups could not meet the local water quality control standard. Finally, suggestions were proposed for water pollution control for the different groups.     

Transformation of ammonium nitrogen and response characteristics of nitrifying functional genes in tannery sludge contaminated soil

High concentrations of ammonium nitrogen released from tannery sludge during storage in open air may cause nitrogen pollution to soil and groundwater. To study the transformation mechanism of NH₄⁺-N by nitrifying functional bacteria in tannery sludge contaminated soils, a series of contaminated soil culture experiments were conducted in this study. The contents of ammonium nitrogen (as NH₄⁺-N), nitrite nitrogen (as NO₂^?-N) and nitrate nitrogen (as NO₃^?-N) were analyzed during the culture period under different conditions of pollution load, soil particle and redox environment. Sigmodial equation was used to interpret the change of NO₃^?-N with time in contaminated soils. The abundance variations of nitrifying functional genes (amoA and nxrA) were also detected using the real-time quantitative fluorescence PCR method. The results show that the nitrification of NH₄⁺-N was aggravated in the contaminated silt soil and fine sand under the condition of lower pollution load, finer particle size and more oxidizing environment. The sigmodial equation well fitted the dynamic accumulation curve of the NO₃^?-N content in the tannery sludge contaminated soils. The Cr(III) content increased with increasing pollution load, which inhibited the reproduction and activity of nitrifying bacteria in the soils, especially in coarse-grained soil. The accumulation of NO₂^?-N contents became more obvious with the increase of pollution load in the fine sand, and only 41.5% of the NH₄⁺-N was transformed to NO₃^?-N. The redox environment was the main factor affecting nitrification process in the soil. Compared to the aerobic soil environment, the transformation of NH₄⁺-N was significantly inhibited under anaerobic incubation condition, and the NO₃^?-N contents decreased by 37.2%, 61.9% and 91.9% under low, medium and high pollution loads, respectively. Nitrification was stronger in the silt soil since its copy number of amoA and nxrA genes was two times larger than that of fine sand. Moreover, the copy numbers of amoA and nxrA genes in the silt soil under the aerobic environment were 2.7 times and 2.2 times larger than those in the anaerobic environment. The abundance changes of the amoA and nxrA functional genes have a positive correlation with the nitrification intensity in the tannery sludge-contaminated soil.     

Is filter packing important in a small-scale vermifiltration process of urban wastewater?

Nowadays, natural resources are under increasing stress which fosters wastewater reuse planning and emphasizes on the decentralized wastewater treatment. Vermifiltration has been described as a viable alternative to treat domestic and urban wastewater, but few studies have focused on the impact of different filter packings on vermifiltration performance. This study evaluates the effect of vermicompost and sawdust in a single-stage vermifilter (VF) for urban wastewater treatment. After an acclimation period of 45 days, urban wastewater from a combined sewage collection system was applied continuously for 24 h. Earthworm stock density was of 20 g L^?1, HRT of 6 h, HLR of 0.89 m³ m^?2 day^?1 and OLR of 7.38 g BOD₅ day^?1. System performance was assessed by the removal efficiencies of BOD₅, COD, TSS, NH₄ ⁺, TN and TP, and fecal coliforms and helminth eggs elimination. Vermicompost (VE) and sawdust (SE) were tested, using an earthworm abundance of 20 g L^?1. Treatment efficiencies were 91.3% for BOD₅, 87.6% for COD, 98.4% for TSS and 76.5% for NH₄ ⁺ in VE, and 90.5% for BOD₅, 79.7% for COD, 98.4% for TSS and 63.4% for NH₄ ⁺ in SE. Earthworms contributed to reduce NH₄ ⁺ and TN removal and to increase NO₃ ^? concentration. No treatment was able to eliminate fecal coliforms down to guidelines values for wastewater irrigation as helminth eggs were completely eliminated. Single-stage vermifiltration system using both filter packings is inconsistent and cannot meet EU guideline values for discharge in sensitive water bodies and WHO guidelines for irrigation with treated wastewater.     

Raw and calcination-modified coal waste as adsorbents to remove cadmium from simulated mining wastewater

The adsorption of cadmium from simulated mining wastewater by coal waste (CW) and calcination-modified coal waste (MCW) was investigated. Effects of pH, initial concentration, particle size of adsorbent, adsorbent dosage and temperature were studied in batch experiments. The adsorption efficiency for cadmium increased with increasing pH, and the optimum pH for cadmium adsorption onto MCW and CW was 6.0 and 6.5, respectively. Kinetic experiments showed that the adsorption equilibrium was reached within 120 min and followed pseudo-second-order model well. The adsorption isotherm data fit Langmuir and Freundlich models, and the adsorption capacity of cadmium on the two adsorbents increased with increasing temperature from 298 to 318 K. MCW had a higher adsorption capacity of cadmium than CW, because calcination treatment can make CW to have more loose structure and higher specific surface area. Thermodynamic parameters, the Gibbs free energy change (?G⁰), enthalpy change (?H⁰) and entropy change (?S⁰), were calculated and the results showed that the adsorption of cadmium on CW and MCW was spontaneous and endothermic. Fourier transform infrared studies indicated silanol and aluminol groups were responsible for cadmium binding. The desorption results indicated that the two adsorbents could be used repeatedly at least three times without significant decrease in the adsorption capacity for cadmium. The results suggested that modified CW could have high potential as low-cost adsorbent for cadmium removal.     

Distribution and isotope composition of nitrogen in Bay of Quinte (Lake Ontario) sediments

The concentrations and isotopic compositions of the various forms of nitrogen in silty clay sediments from the Bay of Quinte (Lake Ontario) have been determined. The total organic-N content is high throughout the sediment profiles and generally decreases with depth. On the contrary, exchangeable NH⁺₄-N concentration is quite low and tends to increase with depth in two out of three sediment cores examined. The concentration of non-exchangeable NH⁺₄-N and the 6 N HCl hydrolyzable NH⁺₄-N are relatively constant with depth. Among the N fractions analyzed, the exchangeable NH⁺₄-is most enriched in ¹⁵N. In most cases, the δ ¹⁵ N values of the N fractions remain relatively constant with sediment depth. There is no apparent correlation of δ ¹⁵ N values with the N concentration for any of the individual N fractions. The observed ranges in the δ ¹⁵ N values are: exchangeable NH⁺₄, + 5–+10‰; 6 N HCl hydrolyzable total N and 6 N HCl hydrolyzable NH⁺₄-N, + 3.5–+5.5‰.     

The impacts of common ions on the adsorption of heavy metal

Researches on the impact of common ions onto sediments are of great importance for the study of the heavy metal adsorption mechanisms. Considering the surface sediments from the relatively clean reach in the Baotou section of the Yellow River as the adsorbent, this work presents the impacts of common ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, Cl⁻, SO₄ ²⁻, and NH₄ ⁺) on heavy metals (Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺) adsorption. The experimental results reveal that the adsorptive capacities of the heavy metals are controlled by different adsorption mechanisms in different ion concentration ranges. With the increase of the ionic strength, the adsorption of the heavy metals increases for the compression of the electric double layer, whereas decreases for the decreasing of the ionic activities of the heavy metals. The competitive adsorption and complexations between the heavy metals and common ions are also important factors controlling the heavy metal adsorption. According to the experimental results and the real concentration of common ions in the Baotou section of the Yellow River, the increase of the concentrations of Na⁺, Mg²⁺, K⁺, and Ca²⁺ would cause the increase of Zn²⁺ adsorption and reduce the Zn pollution. The NH₄ ⁺ from the industrial discharge of the tributaries has a strong impact on the heavy metal adsorption.     

Treatment of polluted river water by a gravel contact oxidation system constructed under riverbed

The objective of this study was to evaluate the treatment efficiency of a gravel contact oxidation treatment system which was newly constructed under the riverbed of Nan-men Stream located at the Shin Chu City of Taiwan. The influent and effluent water samples were taken periodically for the analyses of pH, temperature, dissolved oxygen, total suspended solids, five-day biological oxygen demand, NH₄ ⁺-N. The results showed that the average removal rates of five-day biological oxygen demand, total suspended solids and NH₄ ⁺-N were 33.6% (between ?6.7% and 82.1%), 56.3% (between ?83.0% and 93.4%) and 10.7% (between ?13.0% and 83.3%), respectively. The calculated mean first order reaction rate constant for five-day biological oxygen demand was 4.58/day with a standard deviation of 4.07/day and for NH₄ ⁺-N was 2.15/day with a standard deviation of 5.68/day. Therefore, it could be said that this gravel-contact-oxidation system could effectively remove biological oxygen demand, total suspended solids, and NH₄ ⁺-N in river water at a relatively short hydraulic retention time, although its pollutant treatment efficiency was not quite stable. However, to reach better or more stable treatment efficiency, aeration might sometimes be necessary to increase the dissolved oxygen in influent river water. And, longer hydraulic retention time of the system might also be required to increase NH₄ ⁺-N removal efficiency.     

The impact of sewage-contaminated river water on groundwater ammonium and arsenic concentrations at a riverbank filtration site in central Delhi,India

The groundwater abstracted at a well field near the Yamuna River in Central Delhi, India, has elevated ammonium (NH₄ ⁺) concentrations up to 35 mg/L and arsenic (As) concentrations up to 0.146 mg/L, constituting a problem with the provision of safe drinking and irrigation water. Infiltrating sewage-contaminated river water is the primary source of the NH₄ ⁺ contamination in the aquifer, leading to reducing conditions which probably trigger the release of geogenic As. These conclusions are based on the evaluation of six 8–27-m deep drillings, and 13 surface-water and 69 groundwater samples collected during seven field campaigns (2012–2013). Results indicate that losing stream conditions prevail and the river water infiltrates into the shallow floodplain aquifer (up to 16 m thickness), which consists of a 1–2-m thick layer of calcareous nodules (locally known as kankar) overlain by medium sand. Because of its higher hydraulic conductivity (3.7 × 10^?3 m/s, as opposed to 3.5 × 10^?4 m/s in the sand), the kankar layer serves as the main pathway for the infiltrating water. However, the NH₄ ⁺ plume front advances more rapidly in the sand layer because of its significantly lower cation exchange capacity. Elevated As concentrations were only observed within the NH₄ ⁺ plume indicating a causal connection with the infiltrating reducing river water.     

Treatment of polluted river water by a new constructed wetland

A new constructed wetland was built to purify one polluted river in Taiwan, and this study was conducted to evaluate the treatment efficiency of the wetland. Due to the very limitation of available budget, several water quality items, which were stipulated by Taiwan’s Environmental Protection Administration for rivers, in the influent and effluent of wetland were analyzed and evaluated. These items included water temperature, pH, DO, BOD₅, TSS, and NH₄ ⁺-N. The results showed that the average removal rates of total (unfiltered) BOD₅, TSS and NH₄ ⁺-N were 36.9 %, 71.8 % and 47.1%, respectively. With the HRT more than 3.4 days, the wetland could treat the polluted river water effectively. Longer HRT in this wetland appeared no obvious improvement on the removal rate of TSS or NH₄ ⁺-N. However, BOD removal rate increased while the HRT (Hydraulic Retention Time) increased to about 5 days. In this wetland, the calculated mean first-order reaction rate constant (k_T) for BOD₅ was 0.15/day with a standard deviation of 0.13/day and for NH₄ ⁺-N was 0.24/ day with a standard deviation of 0.18/day. It is also concluded that there is a linear proportional relationship between BOD concentrations in the effluent of wetland and its influent mass loading rates, with the coefficient of determination (R²) of 0.6511. Similar result was seen for NH₄ ⁺-N as well, with the coefficient of determination (R²) of 0.5965. TSS removal rate was found to be linearly proportional to its influent mass loading rate, with the coefficient of determination (R²) of 0.4875.     

Study on Nitrogen Dynamics at the Sediment–Water Interface of Dongting Lake,China

Eutrophication of lakes and reservoirs has become a worldwide environmental problem, and nitrogen (N) has been recognized as one of the key factors responsible for eutrophication. Nitrogen adsorbed on sediments may be released via chemical and biological processes under changing environmental conditions. Spatial distributions of concentrations of ammonia nitrogen (NH₄ ⁺–N), nitrate nitrogen (NO₃ ^?–N) and total nitrogen (TN) were investigated in sediments and overlying water of Dongting Lake, the second largest freshwater lake in China. The concentration of TN in the sediments exhibited strong spatial variation with relatively high values in the eastern part and relatively low values in the southern part of the lake. The TN concentration in the water of different regions of Dongting Lake was affected by the internal load of sediment N. The vertical distribution of TN in sediment cores showed a decreasing trend with an increase in depth. Concentrations of NH₄ ⁺–N in the sediment cores decreased with the depth increase until 6–8 cm and then increased slowly. However, concentrations of NO₃ ^?–N in the sediment cores showed an opposite trend from those of NH₄ ⁺–N. A kinetic release experiment of NH₄ ⁺–N showed that the maximum release rate occurred in the first 5 min and the amount of NH₄ ⁺–N release reached 77.93–86.34 % of the total amount in 0–10 min. The release of NH₄ ⁺–N in the surface sediments of Dongting Lake fits a first-order kinetics function.     

Effects of sediment texture on in-stream nitrogen uptake

A comparative experiment was conducted in two cross sections with sandy and sandy loam sediment textures along an agricultural drainage stream in eastern China to address the effects of sediment texture on in-stream nitrogen uptake efficiency. Using dimerous chambers for in situ incubations, NO₃-N and NH₄-N uptake metrics (i.e., areal uptake rate and uptake velocity) and associated hydrochemical variables in the enclosed sediment–water column system were measured for 8 days and two nights across April–July in 2011 and March–June in 2012. For the investigated sites, in-stream uptake accounted for 2–45 and 9–36 % of the initial NH₄-N and NO₃-N within the enclosed water column, respectively. Although similar daytime, diel and day-to-day (daytime) variation patterns of NO₃-N or NH₄-N uptake metrics were observed for the two sites, the sandy loam sediments had average net NO₃-N and NH₄-N uptake efficiency ~50 % higher and ~40 % lower than for the sandy sediments, respectively. As NO₃-N was the dominant nitrogen form in the studied water columns (typical of agricultural drainage rivers), the sandy loam sediment site had an average of about 47 % higher net uptake efficiency for dissolved inorganic nitrogen (i.e., NO₃-N + NH₄-N). This study demonstrates that sediment texture has a considerable effect on spatial variation of nitrogen uptake along the river system. Changing sediment texture due to anthropogenic modifications on catchment land use and stream channels has the potential to change stream nitrogen cycling as well as altering nitrogen inputs and forms to downstream aquatic ecosystems.     

The abundance of ammonium in the granites of central Spain,and the behaviour of the ammonium ion during anatexis and fractional crystallization

Summary The granites of the Sistema Central Espanol are richer in ammonium than those of most other regions, and have a mean NH₄ ⁺ content of 84 ppm (range = 1–243 ppm). Among the possible causes for the high level of ammonium, a high proportion of organic-rich pelitic protolith and reducing conditions during anatexis are considered to be the most significant. The behaviour of the ammonium ion during magmatic differentiation is discussed by reference to its distribution in the Pedrobernardo layered intrusion: ammonium is depleted in the final liquid fraction, but there is no relative fractionation of NH₄ ⁺ and K⁺. The depletion of the melt in NH₄ ⁺ during crystallization is attributed to its removal by biotite and to a lesser extent by K-feldspar. The behaviour of the ammonium ion during anatexis is discussed with reference to the Peña Negra migmatite complex. It is shown that large amounts of NH₄ ⁺ are present in these high grade metamorphic rocks, and that NH₄ ⁺ is preferentially partitioned into the restite fraction during partial melting. These relationships are attributed to the preferential incorporation of NH₄ ⁺ into potassic host minerals in the order: biotite > muscovite > K-feldspar.

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Ammonium in Zentralspanischen Graniten, und das Verhalten des Ammonium-Ions während Anatexis und fraktionierter Kristallisation

Zusammenfassung Die Granite des Sistema Central Espanol sind reicher an Ammonium als die der meisten anderen Regionen, und haben einen durchschnittlichen NH₄ ⁺ Gehalt von 84 ppm (von 1-243 ppm). Der hohe Ammoniumgehalt könme auf einen hohen Anteil peiitischer Ausgangsgesteine, die reich an organischen Material sind, and auf reduzierende Bedingungen während der Anatexis zurückgehen. Das Verhalten des Ammonium-Ions während magmatischer Differentiation wind in Hinblick seiner Verteilung in der geschichteten Intrusion von Pedrobernardo diskutiert: Ammonium ist in der finalen Schmelzfraktion angereichert, aber es gibt keine relative Fraktionierung von NH₄ ⁺ and K⁺. Die Verarmung der Schmelze an NH₄ ⁺ wahrend der Kristallisation geht darauf zurück, daß NH₄ ⁺ von Biotit and in einem geringen Ausmaß von K-Feldspat aufgenommen wird. Das Verhalten des Ammonium-Ions während der Anatexis wird am Peña Negra Migmatit-Komplex diskutiert. Es zeigt rich, daß große Mengen von NH₄ ⁺ in diesen hochgradig metamorphen Gesteinen vorkommen, and das NH₄ ⁺ während teilweiser Aufschmelzung vorzugsweise in der Restit-Fraktion angereichert wird. Diese Beziehungen gehen auf die vorzugsweise Aufnahme von NH₄ ⁺ in Kali-führenden Gastmineralen zurück, and zwar in folgender Ordnung: Biotit > Muskovit > K-Feldspat.

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With 5 Figures     

Thermal decomposition of NH4-analcime

The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH₄-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH₄⁺ molecule onto NH₃ and proton (framework OH group) and diffusion of NH₃ out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH₃ desorption is estimated to be 145(±13) kJ mol^–1. This value is within the upper limit of the activation energy characteristic for the NH₃ desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH₃ and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol^–1.     

Reversibility of radiocaesium sorption on illite

Adsorption of trace amounts of radiocaesium on NH₄-, K-, and Na-saturated Fithian illite and subsequent desorption by 1 M NH₄ showed that a substantial amount of radiocaesium (44%, 46%, and 91% for NH₄-, K-, and Na-illite, respectively) cannot be desorbed after only 5 min of adsorption. Our results suggest that this instantaneous fixation is caused by the collapse of the frayed edges of the clay mineral and the relatively high concentration of radiocaesium building up in solution in the batch desorption experiments. Consequently, commonly applied high-NH₄ extractions underestimate truly exchangeable amounts of radiocaesium in soils and sediments containing illitic clay minerals. The rate of desorption of trace amounts of radiocaesium from the solids using high NH₄ or Cs concentrations has a half-life of about 2 yr, reflecting radiocaesium desorption from (partially) collapsed interlayers. Extraction of radiocaesium from illite after 5 min of contact time with a Cs-selective adsorbent or a 1 × 10^-6 M CsCl solution shows that 100% of the bound radiocaesium is readily available. The desorption rate in the presence of a Cs-selective adsorbent has a half-life of about 0.2 yr. Desorption of radiocaesium from illite using different ammonium concentrations shows that radiocaesium partitioning follows reversible ion-exchange theory if the NH₄ concentration is below 1 × 10^-4 M, and sufficient time (weeks) is allowed for the reaction to proceed. Thus, radiocaesium sorption reversibility in the natural environment is much higher than generally assumed, and equilibrium solid/liquid partitioning may be assumed for the long-term modelling of radiocaesium mobility in the natural environment. In the particular case of anoxic freshwater sediments with very high NH₄ concentrations in the pore waters (up to several mmol.L^-1), collapse of the frayed edges of illite may occur, influencing radiocaesium partitioning. If collapse occurs before radiocaesium adsorbs to illite, high caesium sorption reversibility as measured by high-NH₄ extraction can be expected because further collapse of the frayed edges during the extraction procedure will be limited. This effect has indeed been observed earlier in the extraction of radiocaesium from anoxic freshwater sediments with high-NH₄ solutions and was as yet unexplained.     

Mechanism of efficient nutrient removal and microbial analysis of a combined anaerobic baffled reactor–membrane bioreactor process

A combined ABR–MBR process consisting of an anaerobic baffled reactor (ABR) combined with an aerobic membrane bioreactor (MBR) treating municipal wastewater was investigated at controlled pH range 6.5–8.5 and at constant temperature 25 ± 1 °C. Total nitrogen (TN), ammonia (NH₄ ⁺–N), total phosphorus (TP), and chemical oxygen demand (COD) removal performances were evaluated by analyzing the mechanism for efficient nutrient removal. The results showed that the average removal rates of COD, NH₄ ⁺–N, TN, and TP reached 93, 99, 79, and 92 %, respectively, corresponding with the COD, NH₄ ⁺–N, TN, and TP effluent of 24 (18–31), 0.4 (0–0.8), 10.6 (8.8–12.9), and 0.31 (0.1–0.5) mg/L under the operational condition of hydraulic retention time (HRT) 7.5 h, recycle ratio 200 %, and dissolved oxygen 3 mg/L. The MBR enhanced NH₄ ⁺–N, TN, and TP removal rates of 13, 10, and 18 %, respectively, and the membrane retention reduced TP 0.17 mg/L. The process was able to maintain a stable performance with high-quality effluent. Analysis of the results by fluorescence in situ hybridization showed that the abundance of ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, and phosphorus accumulating organisms as percentages of all bacteria in each compartment was stable. The enriched microorganisms in the system appear to be the main drivers of the process efficient for nutrient removal.